WO2019026593A1 - Water repellent composition - Google Patents

Abstract

Provided is a water repellent composition which does not use a fluorine-containing monomer, especially a fluoroalkyl group-containing monomer. A water repellent composition which contains (1) (a) a polymer which has a repeating unit derived from an amide group-containing monomer that is represented by formula AA (wherein R1 represents an organic residue having an ethylenically unsaturated polymerizable group; R2 represents a hydrocarbon group having 7-30 carbon atoms; and R3 represents a hydrocarbon group having 1-5 carbon atoms) in an amount of 2-100% by weight relative to the polymer, and (2) a liquid medium.

Description

Water repellent composition

The present invention relates to a water repellent composition.

Conventionally, fluorine-containing water and oil repellents comprising a fluorine compound are known. This water and oil repellent agent exhibits good water and oil repellency when it is treated on a substrate such as a fiber product.
Recent research results [EPA report [PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENT TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROO OCTANOIC ACID AND ITS SALTS] (http://www.epa.gov/opptintr/pfoa/pfoara.pdf) etc Concerns about environmental impact on PFOA (perfluorooctanoic acid), which is a kind of fluoroalkyl compound, are becoming clear, and EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA on April 14, 2003 I announced.
Meanwhile, Federal Register (FR Vol. 68, No. 73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr. Pdf) and EPA Environmental News FOR RELEASE : MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoamacts. pdf) has published that telomers may generate PFOA by decomposition or metabolism (telomers mean long chain fluoroalkyl groups). We also announce that telomers are used in many products such as water and oil repellent, stain resistant foam, care products, cleaning products, carpets, textiles, paper and leather. There is. It is feared that fluorine-containing compounds accumulate in the environment.

JP-A-2006-328624 is a water repellent comprising a non-fluorinated polymer containing, as a monomer unit, a (meth) acrylic ester having 12 or more carbon atoms in the ester portion, which is a (meth) acrylic ester Discloses a water repellent having a composition ratio of 80 to 100% by mass with respect to the total amount of monomer units constituting the non-fluorinated polymer.
However, this water repellent is inferior in water repellency.
WO2015 / 076347 discloses a surface treatment agent comprising a non-fluorinated polymer consisting of long chain (meth) acrylate ester monomer and an amidoamine surfactant, and WO2015 / 080026 contains a single amount of long chain (meth) acrylate ester Disclosed is a surface treatment agent comprising a (meth) acrylate monomer having a body and a cyclic hydrocarbon group. In these surface treatment agents, fluoroalkyl group-containing monomers are not used.

JP, 2006-328624, A WO2015 / 076347 (Japanese Patent Application No. 2013-241865) WO 2015/080026 (Japanese Patent Application 2013-241980)

An object of the present invention is to provide a water repellent composition which gives excellent water repellency and does not use a fluoroalkyl group-containing monomer, preferably a fluorine-containing monomer.

The present invention
formula:

[Wherein, R ¹ represents an organic residue having an ethylenically unsaturated polymerizable group,
R ² is a hydrocarbon group having 7 to 30 carbon atoms,
R ³ is a hydrocarbon group having 1 to 5 carbon atoms. ]
The present invention relates to a polymer having a repeating unit derived from an amide group-containing monomer represented by
According to one gist, the present invention
(1) (a) 2 to 100% by weight of the polymer, the formula:

[Wherein, R ¹ represents an organic residue having an ethylenically unsaturated polymerizable group,
R ² is a hydrocarbon group having 7 to 30 carbon atoms,
R ³ is a hydrocarbon group having 1 to 5 carbon atoms. ]
The present invention provides a water repellent composition comprising a polymer having a repeating unit derived from an amide group-containing monomer represented by the formula: and (2) a liquid medium.

Since the water repellent composition of the present invention does not use a fluoroalkyl group-containing monomer, there is no concern of accumulation of the fluorine-containing compound in the environment. The water repellent composition of the present invention gives the substrate excellent water repellency.
The stability (emulsion stability) of the water repellent composition of the present invention is good. The water repellent composition of the present invention is excellent in water- and oil-repellent (in particular, water-repellent) durability (in particular, washing durability). Furthermore, the processing stability at the time of the water repellent treatment is excellent.

The water repellent composition comprises (1) a polymer and (2) a liquid medium. The water repellent composition may further contain (3) a surfactant.

(1) Polymer The polymer of the present invention is a polymer having no fluoroalkyl group. The polymer of the present invention is preferably a non-fluorinated polymer having no fluorine atom.
In the present invention, the polymer is
(A) having a repeating unit derived from an amide group-containing monomer.
The polymer may further be a repeating unit derived from a polymerizable monomer other than the amide group-containing monomer (a), preferably a non-fluorinated polymerizable monomer other than the monomer (a). You may have.

The polymerizable monomer other than the monomer (a) may be a non-fluorine non-crosslinkable monomer or a non-fluorine crosslinkable monomer.
The non-fluorine non-crosslinkable monomer has the formula:
CH ₂ = CA-T
[Wherein, A represents a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a halogen atom other than a fluorine atom (eg, chlorine atom, bromine atom and iodine atom), a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chain or ring having an ester bond It is an organic group having 2 to 41 carbon atoms. ]
It may be a compound represented by

Examples of the linear or cyclic hydrocarbon group having 1 to 40 carbon atoms include linear or branched, saturated or unsaturated (for example, ethylenically unsaturated) aliphatic hydrocarbon groups having 1 to 40 carbon atoms, and having carbon atoms It is a saturated or unsaturated (eg, ethylenically unsaturated) cyclic aliphatic group of 4 to 40, an aromatic hydrocarbon group of 6 to 40 carbon atoms, and an aromatic aliphatic hydrocarbon group of 7 to 40 carbon atoms.

Examples of the chain-like or cyclic C2-C41 organic group having an ester bond include -C (= O) -OQ and -OC (= O) -Q (wherein Q represents 1 to 40 carbon atoms). Straight-chain or branched, saturated or unsaturated (for example, ethylenically unsaturated) aliphatic hydrocarbon group, saturated or unsaturated (for example, ethylenically unsaturated) cyclic aliphatic group having 4 to 40 carbon atoms, carbon And 6 to 40 aromatic hydrocarbon groups and C7 to C40 araliphatic hydrocarbon groups).

The non-fluorine crosslinking monomer is as described later.

Examples of polymerizable monomers other than the monomer (a) are as follows.
(B) Acrylate ester monomer,
(C) non-fluorine crosslinking monomer, and (d) halogenated olefin.
The polymer may have a fluorine atom, but preferably does not have a fluorine atom. That is, the polymer is preferably a non-fluorinated polymer, and all the monomers are preferably non-fluorinated monomers.

(A) Amide Group-Containing Monomer The amide group-containing monomer has the formula:

[Wherein, R ¹ represents an organic residue having an ethylenically unsaturated polymerizable group,
R ² is a hydrocarbon group having 7 to 30 carbon atoms,
R ³ is a hydrocarbon group having 1 to 5 carbon atoms. ]
It is a compound shown by these.

The amide group-containing monomer does not have a fluoroalkyl group.

R ¹ is an organic residue having an ethylenically unsaturated polymerizable group, and is not particularly limited as long as there is a double bond between carbons. Specific examples thereof include organic residues having an ethylenically unsaturated polymerizable group such as -C (= O) CR ¹¹ = CH ₂ , -CHR ¹¹ = CH ₂ , -CH ₂ CHR ¹¹ = CH _2, etc. ¹¹ includes a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ may have various organic groups in addition to the ethylenically unsaturated polymerizable group, and examples thereof include organic groups such as chain hydrocarbon, cyclic hydrocarbon, polyoxyalkylene group and polysiloxane group. These organic groups may be substituted with various substituents.
R ² is a hydrocarbon group having a carbon number of 7 to 30, and examples thereof include chain hydrocarbon, cyclic hydrocarbon and the like. Among them, a chain hydrocarbon is preferable, and a linear saturated hydrocarbon group is particularly preferable. The carbon number of R ² is 7 to 30, preferably 11 to 27, and particularly preferably 15 to 23.
R ³ is a hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms may be linear or branched and may have an unsaturated bond, but is preferably linear. The number of carbon atoms of R ³ is preferably 2 to 4, and particularly preferably 2. R ³ is preferably an alkylene group.

The amide group-containing monomer is one in which R ² is single (for example, only a compound in which R ² has 17 carbon atoms), or one in which R ² is a combination of ^two or more (for example, R ² in carbon number is 17) And a compound in which the carbon number of R ² is 15).

Specific examples of the amide group-containing monomer are: palmitic acid amidoethyl (meth) acrylate, stearic acid amidoethyl (meth) acrylate, behenic acid amidoethyl (meth) acrylate, myristate amidoethyl (meth) acrylate, lauric acid amidoethyl (meth) Acrylate, isostearic acid ethylamide (meth) acrylate, oleic acid ethylamide (meth) acrylate, tertiary butylcyclohexyl caproic acid amidoethyl (meth) acrylate, adamantane carboxylic acid ethylamide (meth) acrylate, naphthalenecarboxylic acid amidoethyl (meth) acrylate, anthracene carbonic Acid amidoethyl (meth) acrylate, palmitic acid amidopropyl (meth) acrylate, stearic acid amide Propyl (meth) acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether, or mixtures thereof.

The amide group-containing monomer is preferably amidoethyl stearate (meth) acrylate. The amide group-containing monomer may be a mixture containing amidoethyl stearate (meth) acrylate. In the mixture containing stearic acid amidoethyl (meth) acrylate, the amount of stearic acid amidoethyl (meth) acrylate is, for example, 55 to 99% by weight, preferably 60 to 85% by weight based on the total weight of the amide group-containing monomer. More preferably, it may be 65 to 80% by weight, and the remaining monomer may be, for example, amidoethyl palmitate (meth) acrylate.

(B) acrylate ester monomer polymer may have the repeating units derived from other acrylate ester monomer.
Examples of other acrylate ester monomers are as follows.
(B1) Acrylate ester monomer having aliphatic hydrocarbon group, and (b2) Acrylate ester monomer having cyclic hydrocarbon group The polymer comprises monomer (b1) and monomer (b2). It may have repeating units derived from at least one monomer selected from the group.

(B1) aliphatic hydrocarbon radical acrylate ester monomer polymer having may have repeating units derived from an aliphatic hydrocarbon group containing acrylate ester monomer. The aliphatic hydrocarbon group-containing acrylate ester monomer is (meth) acrylate ester (i.e., acrylate or methacrylate).
Preferred examples of aliphatic hydrocarbon group-containing acrylate ester monomers have the formula:
CH ₂ = CA ¹¹ -C (= O) -O-A ¹²
[Wherein, A ¹¹ represents a hydrogen atom or a methyl group,
A ¹² is a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms. ]
It is a compound shown by these.

The aliphatic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group. The aliphatic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably contains no fluorine atom.
A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. The linear or branched hydrocarbon group has a carbon number of 1 to 40, for example 10 to 40, preferably 18 to 40. The linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly 18 or 22 carbon atoms, and is preferably a saturated aliphatic hydrocarbon group, particularly an alkyl group.
Specific examples of the aliphatic hydrocarbon group-containing acrylate ester monomer include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.
The presence of the aliphatic hydrocarbon group-containing acrylate ester makes the texture more flexible.

(B2) a cyclic acrylate ester monomer polymer having a hydrocarbon group may have a repeating unit derived from a cyclic hydrocarbon group containing acrylate ester monomer.
The cyclic hydrocarbon group-containing acrylate ester monomer is
formula:
CH ₂ = CA ²¹ -C (= O) -O-A ²²
[Wherein, A ²¹ represents a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (wherein X ¹ and X ² represent a hydrogen atom, A fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl And
A ²² is a cyclic hydrocarbon-containing group having 4 to 40 carbon atoms. ]
It is preferable that it is a compound shown by these.
The cyclic hydrocarbon group-containing acrylate ester monomer is preferably a monomer having a high glass transition temperature of its homopolymer (for example, 50 ° C. or more, particularly 80 ° C. or more).

The cyclic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably contains no fluorine atom.

Examples of A ²¹ are hydrogen atom, methyl group, Cl, Br, I, F, CN, CF ₃ . A ²¹ is preferably a chlorine atom.
A ²² is a cyclic hydrocarbon group which may have a chain group (eg, a linear or branched hydrocarbon group). The cyclic hydrocarbon group includes a saturated or unsaturated monocyclic, polycyclic, bridged cyclic group and the like. The cyclic hydrocarbon group is preferably saturated. The carbon number of the cyclic hydrocarbon group is 4 to 40, preferably 6 to 20. Examples of the cyclic hydrocarbon group include cyclic aliphatic groups having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and aromatic aliphatic groups having 7 to 20 carbon atoms. The carbon number of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group and dicyclopentenyl group.

As specific examples of cyclic hydrocarbon group-containing acrylate ester monomers,
Cyclohexyl acrylate, t-butyl cyclohexyl acrylate, benzyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate; and cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentanyl Examples include methacrylate and dicyclopentenyl methacrylate.
The presence of the cyclic hydrocarbon group-containing acrylate ester monomer can improve processing stability and improve water repellency.

(C) a non-fluorinated crosslinking monomer polymer may have the repeating units derived from fluorine-free crosslinkable monomer.
The non-fluorine crosslinkable monomer is a monomer which does not contain a fluorine atom. The non-fluorine crosslinking monomer may be a compound having at least two reactive groups and / or ethylenic carbon-carbon double bonds (preferably, a (meth) acrylate group) and not containing fluorine. The non-fluorine crosslinking monomer may be a compound having at least two ethylenic carbon-carbon double bonds (preferably, a (meth) acrylate group), or at least one ethylenic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups and the like.

The non-fluorine crosslinkable monomer may be a mono (meth) acrylate having a reactive group, a di (meth) acrylate or a mono (meth) acrylamide. Alternatively, the non-fluorine crosslinkable monomer may be di (meth) acrylate.

One example of the non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.
As the non-fluorine crosslinking monomer, for example, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2,3 -Dihydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate , 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. , It is not limited thereto.

The presence of the non-fluorine crosslinkable monomer increases the washing durability given by the polymer.

(D) The halogenated olefin monomer copolymer may have a repeating unit derived from a halogenated olefin monomer.
The halogenated olefin monomer preferably has no fluorine atom.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms which is substituted by 1 to 10 chlorine atom, bromine atom or iodine atom. The halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having a chlorine atom of 1 to 5 carbon atoms. Preferred specific examples of halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide and vinylidene iodide. Vinyl chloride is preferred because the water repellency (in particular, the durability of the water repellency) is enhanced.
The presence of the halogenated olefin increases the washing durability provided by the polymer.

(E) Other Monomers Monomers Other monomers (a) to (d) (e), for example, non-fluorine non-crosslinkable monomers may be used.
Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate And vinyl alkyl ethers. Other monomers are not limited to these examples.

As used herein, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

Each of the monomers (a) to (e) may be one kind alone, or may be a mixture of two or more kinds.

The amount of monomer (a) is 2 to 100% by weight, based on the polymer. The lower limit of the amount of monomer (a) may be 3% by weight, for example 5% by weight, in particular 10% by weight, in particular 15% by weight, based on the polymer. Alternatively, the lower limit of the amount of monomer (a) may be 20% by weight, for example 25% by weight, in particular 30% by weight, especially 40% by weight or 50% by weight, relative to the polymer. The upper limit of the amount of monomer (a) may be 95% by weight, for example 80% by weight, alternatively 75% by weight, alternatively 70% by weight, based on the polymer.
In the polymer, 100 parts by weight of the monomer (a)
The amount of the repeating unit (b) is 0 to 2000 parts by weight, preferably 0 to 200 parts by weight, more preferably 1 to 100 parts by weight, for example 5 to 80 parts by weight,
The amount of the repeating unit (c) is 0 to 50 parts by weight, preferably 1 to 10 parts by weight, for example 2 to 8 parts by weight,
The amount of the repeating unit (d) is 0 to 100 parts by weight, preferably 1 to 60 parts by weight, for example 2 to 10 parts by weight,
The amount of the repeating unit (e) is 0 to 100 parts by weight, preferably 1 to 30 parts by weight, for example 2 to 10 parts by weight,
It may be.
In the polymer, the amount of each of the monomer (b1) and the monomer (b2) is 0 to 150 parts by weight, preferably 1 to 100 parts by weight, with respect to 100 parts by weight of the monomer (a) For example, it may be 2 to 50.
Alternatively, the amounts of the monomer (b), the monomer (c), the monomer (d) and the monomer (e) are, relative to the polymer, (b): (c): (d) (E) 0 to 80% by weight: 0 to 10% by weight: 0 to 40% by weight: 0 to 20% by weight, for example 3 to 75% by weight: 0.5 to 5% by weight: 2 to 30% by weight: It may be from 0 to 10% by weight, in particular 10 to 70% by weight: 0.8 to 3% by weight: 5 to 25% by weight: 0 to 5% by weight.

The number average molecular weight (Mn) of the polymer may generally be from 1,000 to 1,000,000, such as from 5,000 to 500,000, in particular from 3,000 to 200,000. The number average molecular weight (Mn) of the polymer is generally measured by GPC (gel permeation chromatography).

In the present invention, the monomer is polymerized to obtain a water repellent composition in which the polymer is dispersed or dissolved in a liquid medium.
The monomers used in the present invention are as follows.
Monomer (a),
Monomer (a) + (b),
Monomer (a) + (b) + (c),
Monomer (a) + (b) + (d), or Monomer (a) + (b) + (c) + (d).
In addition to the above, monomers (e) may be used. The monomer (b) may be at least one of the monomers (b1) and (b2).

(2) Liquid Medium The water repellent composition contains a liquid medium. The liquid medium is water, an organic solvent or a mixture of water and an organic solvent.
The water repellent composition is generally a solution or a dispersion. The solution is a solution in which the polymer is dissolved in an organic solvent. A dispersion is an aqueous dispersion in which a polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent).
Examples of the organic solvent are esters (eg, esters having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (eg, ketones having 2 to 30 carbon atoms, specifically, methyl ethyl ketone, diisobutyl) Ketones, alcohols (eg, alcohols having 1 to 30 carbon atoms, specifically isopropyl alcohol), aromatic solvents (eg, toluene and xylene), petroleum solvents (eg, alkanes having 5 to 10 carbon atoms, Specifically, naphtha and kerosene).
The liquid medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of organic solvent may be up to 30% by weight, for example up to 10% by weight (preferably up to 0.1% by weight), based on the liquid medium. The liquid medium is preferably water alone.

(3) Surfactant When the water repellent composition is an aqueous dispersion, it preferably contains a surfactant.
In the water repellent composition of the present invention, the surfactant contains a nonionic surfactant. Furthermore, the surfactant preferably includes one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. It is preferred to use a combination of nonionic surfactant and cationic surfactant.

(3-1) Nonionic Surfactant Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.
An example of an ether is a compound having an oxyalkylene group (preferably, a polyoxyethylene group).
An example of an ester is an ester of an alcohol and a fatty acid. Examples of the alcohol are monohydric to hexavalent (especially divalent to pentavalent) C 1 -C 50 (especially C 10-30) alcohols (eg, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.
An example of an ester ether is a compound obtained by adding an alkylene oxide (particularly ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of the alcohol are monohydric to hexavalent (especially divalent to pentavalent) C1-C50 (especially C3-C30) alcohols (eg, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.

Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamino. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
The polyhydric alcohol may be a divalent to pentavalent alcohol having 10 to 30 carbon atoms.
The amine oxide may be an oxide (for example, 5 to 50 carbon atoms) of an amine (a secondary amine or preferably a tertiary amine).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The carbon number of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the nonionic surfactant molecule is generally preferably 2 to 100.
The nonionic surfactant is selected from the group consisting of ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide, and is preferably a nonionic surfactant having an oxyalkylene group.
The nonionic surfactant is an alkylene oxide adduct of linear and / or branched aliphatic (saturated and / or unsaturated) group, linear and / or branched fatty acid (saturated and / or unsaturated) And polyalkylene oxide esters of polyoxyethylene (POE) / polyoxypropylene (POP) (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, and the like. Among these, the structure of the alkylene oxide addition moiety and the polyalkylene glycol moiety is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (even as a random copolymer, a block copolymer Is preferred).
Further, the nonionic surfactant preferably has a structure not containing an aromatic group in view of environmental problems (biodegradability, environmental hormones, etc.).

The nonionic surfactant has the formula:
R ¹ O- (CH ₂ CH ₂ O) _p- (R ² O) _q -R ³
[Wherein, R ¹ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group,
Each R ² is independently the same or different and is an alkylene group having 3 or more carbon atoms (eg, 3 to 10),
R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms,
p is a number of 2 or more,
q is a number of 0 or 1 or more. ]
It may be a compound represented by
R ¹ preferably has 8 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms. Preferred examples of R ¹ include lauryl group, tridecyl group and oleyl group.
Examples of R ² are a propylene group and a butylene group.
In the nonionic surfactant, p may be a number of 3 or more (eg, 5 to 200). q may be a number of 2 or more (eg, 5 to 200). That is,-(R ² O) _q- may form a polyoxyalkylene chain.
The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (in particular, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain and the like, among which an oxypropylene chain is preferable.

Specific examples of the nonionic surfactant, ethylene oxide and hexyl phenol, isooctanoate butylphenol, hexadecanol, oleic acid, alkane _(C 12 _{-C 16)} thiol, sorbitan mono fatty acid _(C 7 _{-C 19)} or alkyl Condensation products with (C ₁₂ -C ₁₈ ) amines and the like are included.

The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, in particular 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).
The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000.
The nonionic surfactant may be one kind alone, or may be a mixture of two or more kinds.

(3-2) Cationic Surfactant The cationic surfactant is preferably a compound having no amide group.

The cationic surfactant may be amine salt, quaternary ammonium salt, oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, Examples thereof include quaternary ammonium salt type surfactants such as alkyldimethyl benzyl ammonium salt, pyridinium salt, alkyl isoquinolinium salt, benzethonium chloride and the like.

Preferred examples of cationic surfactants are
^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -
[Wherein, R ²¹ , R ²² , R ²³ and R ^{24 each} represents a hydrocarbon group having 1 to 30 carbon atoms,
X is an anionic group. ]
Is a compound of
Specific examples of R ²¹ , R ²² , R ²³ and -R ²⁴ are alkyl groups (eg, methyl group, butyl group, stearyl group, palmityl group). Examples of X are halogen (eg chlorine), acid (eg hydrochloric acid, acetic acid).
The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (C4-30 alkyl alkyl).

The cationic surfactant is preferably an ammonium salt. Cationic surfactants have the formula:
_{^{R 1 p - N + R 2}} q X -
[Wherein, R ¹ represents a C12 or higher (eg, C ₁₂ -C ₅₀ ) linear and / or branched aliphatic (saturated and / or unsaturated) group,
R ² is H or a C 1-4 alkyl group, a benzyl group or a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (especially 2, particularly 3) to 50)
(CH ₃ and C ₂ H ₅ are particularly preferred),
X is a halogen atom (eg, chlorine), a C ₁ to C ₄ fatty acid base,
p is 1 or 2, q is 2 or 3, and p + q = 4. ]
It may be an ammonium salt represented by The carbon number of R ¹ may be 12 to 50, for example 12 to 30.

Specific examples of cationic surfactants include dodecyl trimethyl ammonium acetate, trimethyl tetradecyl ammonium chloride, hexadecyl trimethyl ammonium bromide, trimethyl octadecyl ammonium chloride, (dodecyl methyl benzyl) trimethyl ammonium chloride, benzyl dodecyl dimethyl ammonium chloride, methyl dodecyl Included are di (hydropolyoxyethylene) ammonium chloride, benzyldodecyl di (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride.

Amphoteric surfactants include alanines, imidazolinium betaines, amidobetaines, betaine acetate, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl Aminoacetic acid betaine, fatty acid amidopropyl dimethylaminoacetic acid betaine and the like.

Each of nonionic surfactant, cationic surfactant, and amphoteric surfactant may be one type or a combination of two or more.
The amount of the cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more based on the total amount of the surfactant. The weight ratio of nonionic surfactant to cationic surfactant is preferably 95: 5 to 20:80, more preferably 85:15 to 40:60.
The amount of cationic surfactant may be 0.05 to 10 parts by weight, such as 0.1 to 8 parts by weight, based on 100 parts by weight of the polymer. The total amount of surfactant may be 0.1 to 20 parts by weight, for example 0.2 to 10 parts by weight, with respect to 100 parts by weight of the polymer.

(4) Additive The water repellent composition of the present invention comprises (4) an additive in addition to the fluorine-containing polymer (1) and the liquid medium (2) and optionally (3) a surfactant. It is also good.
Examples of the additive (4) include other water repellents, oil repellents, drying rate regulators, crosslinking agents, coalescents, coalescents, compatibilizers, surfactants, antifreeze agents, viscosity regulators, UV absorbers And antioxidants, pH adjusters, antifoamers, texture modifiers, slip modifiers, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, etc.
The additive (4) may be a fluoropolymer.

The water repellent composition of the present invention may contain only the above-mentioned non-fluorinated polymer as a polymer (active ingredient), but it may also contain a fluorinated polymer in addition to the above-mentioned non-fluorinated polymer Good. Generally, in a water repellent composition (particularly, an aqueous emulsion), particles formed by a non-fluorinated polymer and particles formed by a fluoropolymer are separately present. That is, it is preferable to mix the non-fluorinated polymer and the fluorinated polymer after separately manufacturing the non-fluorinated polymer and the fluorinated polymer. In general, after separately preparing an emulsion of a non-fluorinated polymer (in particular, an aqueous emulsion) and an emulsion of a fluoropolymer (in particular, an aqueous emulsion), the emulsion of a non-fluorinated polymer and an emulsion of a fluorinated polymer are mixed Is preferred.

The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer. The fluorine-containing monomer has a general formula:
_{CH 2 = C (-X) -C} (= O) -Y-Z-Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X are ² represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, Substituted or unsubstituted phenyl group;
Y is -O- or -NH-;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group,
-CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms) or
-CH ₂ CH (OZ ¹ ) CH ₂ -group (wherein Z ¹ is a hydrogen atom or an acetyl group) or
_{- (CH 2) m -SO 2} - (CH 2) n - group or a _{- (CH 2) m -S- (} CH 2) n - group (where, m is 1 ~ 10, n is 0 to 10 in, is there),
R f is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
It is preferable that it is an acrylate ester or acrylamide shown by these.
The carbon number of the Rf group is preferably 1 to 6, particularly 4 to 6, particularly 6.

The fluorine-containing polymer is a repeat derived from at least one non-fluorine monomer selected from the group consisting of a halogenated olefin monomer, a non-fluorine non-crosslinkable monomer and a non-fluorine crosslinkable monomer. It may have a unit.
The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms which is substituted by 1 to 10 chlorine atom, bromine atom or iodine atom. Examples of halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.

Preferred non-fluorine non-crosslinkable monomers have the formula:
CH ₂ = CA-T
[Wherein, A represents a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a linear or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a linear or cyclic organic group having 1 to 20 carbon atoms having an ester bond. ]
It is a compound shown by these. Specific examples of the non-fluorine non-crosslinkable monomer include alkyl (meth) acrylate ester, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Included are acrylates, methoxypolypropylene glycol (meth) acrylates, and vinyl alkyl ethers.

The non-fluorine crosslinkable monomer is a compound having at least two carbon-carbon double bonds (eg, (meth) acrylic group) or has at least one carbon-carbon double bond and at least one reactive group. It may be a compound.

The weight ratio of the non-fluorinated polymer to the fluorinated polymer in the water repellent composition may be 100: 0 to 10:90, for example 90:10 to 20:80, preferably 80:20 to 30:70. .
Each of the non-fluorinated polymer and the fluorinated polymer may be one type of polymer, or may be a combination of two or more types of polymers.
When a combination of a non-fluorinated polymer and a fluorinated polymer is used, performance (in particular, water repellency) equal to or more than that obtained when only a fluorinated polymer is used can be obtained.

The polymer (a polymer having no fluoroalkyl group, particularly a non-fluorinated polymer, and a fluorine-containing polymer, particularly a copolymer having a fluoroalkyl group) in the present invention can be produced by any of conventional polymerization methods, and polymerization The reaction conditions can also be selected arbitrarily. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.
If the water repellent composition of the present invention is an aqueous emulsion, the method for producing a polymer is not limited. For example, after producing a polymer by solution polymerization, removal of a solvent and addition of a surfactant and water can be performed to obtain an aqueous emulsion.

In the solution polymerization, a method is adopted in which the monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, heating and stirring in the range of 30 to 120 ° C. for 1 to 10 hours are carried out. As a polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxy dicarbonate and the like It can be mentioned. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example 0.01 to 10 parts by weight, per 100 parts by weight of the monomer.

The organic solvent is one which is inert to the monomer and dissolves them, for example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (for example, carbon) The ketone may be a ketone of a number of 2 to 30, specifically, methyl ethyl ketone, diisobutyl ketone), an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane and the like. The organic solvent is used in the range of 10 to 2000 parts by weight, for example 50 to 1000 parts by weight, based on 100 parts by weight of the total of monomers.

In emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, polymerization is carried out by stirring in the range of 50 to 80 ° C. for 1 to 10 hours. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble substances such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble compounds such as t-butylperoxypivalate and diisopropylperoxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

In order to obtain a polymer aqueous dispersion excellent in storage stability, the monomer is micronized and polymerized in water using an emulsifying apparatus such as a high-pressure homogenizer or an ultrasonic homogenizer that can impart strong crushing energy. Is desirable. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible, it is preferable to add a compatibilizer that makes the monomers sufficiently compatible, for example, a water-soluble organic solvent or a low molecular weight monomer. Emulsifiability and copolymerizability can be improved by the addition of a compatibilizer.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, 10 to 40 parts by weight may be used. In addition, examples of low molecular weight monomers include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, it may be used in the range of 10 to 40 parts by weight.

In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be varied. Examples of chain transfer agents are mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (in particular, alkyl mercaptan (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite Etc. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of monomers.

The water repellent composition of the present invention may be in the form of a solution, an emulsion (in particular, an aqueous dispersion) or an aerosol, but is preferably a solution or an aqueous dispersion. The water repellent composition comprises a polymer (the active ingredient of the water repellent composition) and a medium (in particular, a liquid medium such as an organic solvent and / or water). The amount of medium may be, for example, 5 to 99.9% by weight, in particular 10 to 80% by weight, based on the water repellent composition.
In the water repellent composition, the concentration of the polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

The water repellent composition of the present invention can be used as an external treatment (surface treatment) or an internal treatment.

When the water repellent composition of the present invention is an external treatment agent, it can be applied to an object to be treated by a conventionally known method. In general, the water repellent composition is dispersed and diluted in an organic solvent or water, and is applied to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating and the like, and dried. Is taken. Also, if necessary, curing may be performed with application of a suitable crosslinking agent (eg, blocked isocyanate). Furthermore, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like can be added to the water repellent composition of the present invention and used in combination. The concentration of the polymer in the treatment solution to be brought into contact with the substrate may be 0.01 to 10% by weight (especially in the case of dip coating), for example 0.05 to 10% by weight.

The objects to be treated with the treating agent composition (water repellent composition) of the present invention include fiber products, stone materials, filters (for example, electrostatic filters), dust masks, parts of fuel cells (for example, gas diffusion) Electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like can be mentioned. Various examples can be mentioned as textile products. For example, natural fibers such as cotton, hemp, wool and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, carbon fibers And inorganic fibers such as asbestos fibers or mixed fibers thereof.

The textile product may be in the form of fiber, cloth or the like.
The water repellent composition of the present invention can also be used as an antifouling agent, a release agent, and a release agent (for example, an internal release agent or an external release agent). For example, the surface of the substrate can be easily peeled from the other surface (the other surface of the substrate or the surface of the other substrate).

The polymer can be applied to the fibrous substrate (e.g., textiles, etc.) by any of the methods known to treat textiles with liquids. When the textile is a cloth, the cloth may be dipped in the solution, or the cloth may be deposited or sprayed with the solution. The treated textile is dried and preferably heated, for example, at 100 ° C. to 200 ° C. to develop water repellency.

Alternatively, the polymer may be applied to the textile by a cleaning method and may be applied to the textile, for example in a laundry application or dry cleaning method.

The textiles to be treated are typically fabrics, including woven, knitted and non-woven fabrics, fabrics and carpets in the form of clothing, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving or the like). The textile material may be natural fibers (eg cotton or wool etc), chemical fibers (eg viscose rayon or rheocel etc) or synthetic fibers (eg polyester, polyamide or acrylic fibers etc), or And mixtures of fibers, such as, for example, mixtures of natural and synthetic fibers. Preferably the textile is a carpet.

Alternatively, the fibrous substrate may be leather. Aqueous solution or aqueous emulsion at different stages of leather processing, for example during wet processing of leather or during leather finishing, in order to render the polymer hydrophobic and oleophobic to the leather You may apply from the thing to the leather.
Alternatively, the fibrous substrate may be paper. The produced polymer may be applied to the preformed paper or may be applied at various stages of papermaking, for example during the drying of the paper.

"Treatment" means applying a treatment agent to a processing object by immersion, spraying, application and the like. By the treatment, a polymer which is an active ingredient of the treatment agent penetrates into the inside of the object to be treated and / or adheres to the surface of the object to be treated.

When the water repellent composition is an internal treatment agent, it can impart water repellency to the resin by being added to the resin, for example, a thermoplastic resin. A water repellent composition can be used when producing a molded article of resin.
The liquid medium is removed from the liquid (solution or dispersion) containing the polymer to obtain a polymer. For example, the polymer can be obtained by reprecipitating the polymer dispersion (aqueous dispersion or organic solvent dispersion) with water or an organic solvent and then drying.

For example, a molded object can be manufactured by the manufacturing method which has the process of mixing resin and a polymer and obtaining a resin composition, and the process of shape | molding a resin composition. It is preferable to manufacture a molded object by melt-kneading using an extruder etc.
Generally, the thermoplastic resin and the polymer are compatible in the molten state. Kneading can be performed by, for example, a conventionally known method such as a single screw extruder, a twin screw extruder, and a roll. The resin composition thus obtained is molded by extrusion molding, injection molding, compression molding, blow molding, pressing or the like. The resin composition is molded into molded articles of various shapes. The obtained molded product may be subjected to a heat treatment in an oven, a drying furnace or the like after the molding processing. The molded article may be a single layer, or two to ten layers, for example, three to five layers.

The molded articles can be used in applications where thermoplastic resins are used, in particular in applications where it is desirable to have excellent ease of wiping against dirt and excellent scratch resistance. Applications of moldings include automobiles (exterior parts and interior parts) (eg, bumpers, instrumental panels, door trims), home appliances (eg, washing machines and refrigerators) (eg, housings, doors in refrigerators, trays) , Vegetable room containers), various cases, buildings (interiors and parts) (for example, handrails, wallpaper, desks, chairs, toilet seats and toilet bars, bathtubs), electronic devices (for example, housings for smartphones), drains , Pipes, dishes, flooring, gasoline tanks, fuel hoses, OA equipment, etc. Above all, interior parts of automobiles, interior parts of home appliances, and buildings are more preferable.

EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.
In the following, parts or percentages or ratios represent parts by weight or percentages by weight unless otherwise stated.
The test procedure is as follows.

Water Repellency Test A treatment solution having a solid concentration of 1.5% was prepared, the cloth was dipped in the test solution, passed through a mangle, and the water repellency was evaluated with a test cloth heat-treated at 160 ° C. for 2 minutes. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in the table described below, water repellence No. Represented by The larger the score, the better the water repellency.

Gum up rate test The polymer dispersion was diluted with hard water B (hardness 16: calcium chloride 1.9425 g, magnesium chloride 0.3975 g, sodium sulfate 4.63 g / water 10 L) so that the solid concentration would be 5% by weight. Prepare 1000 g and put in a pad that can be adjusted to 40 ° C. The mangle is continuously treated with a 20 cm wide and 80 cm long polyester cloth as a loop, and is continuously treated at a mangle pressure of 0.4 MPa for 1 hour. The gum up rate is determined by the following equation.

(Gumup amount to mangle) = (weight before treatment of polyester cloth + weight of diluted liquid before treatment)-(weight after treatment of polyester cloth + weight of diluted liquid after treatment)

(Gum-up rate) = 100 × (gum-up amount to mangle) / (Weight of diluted liquid before treatment)

When the gum up rate is less than 4%, gum up is suppressed (processing stability is good).

Production Example 1
40 g of C18SHA, 0.04 g of lauryl mercaptan and 56 g of toluene were charged in a 200 cc four-necked flask equipped with a nitrogen introduction tube, thermometer, stirrer, and reflux tube, and stirred at room temperature for 30 minutes under a nitrogen stream. Thereafter, a solution of 0.4 g of AIBN (azobisisobutyronitrile) in 4 g of toluene was added, and the temperature was raised to 80 ° C., and a polymerization reaction was performed for 8 hours. After polymerization, toluene was further added to prepare a toluene solution having a solid content concentration of 20%.

Production Examples 2 to 7
Polymerization was carried out in the same manner as in Production Example 1 with the composition shown in Table 1. After polymerization, the solution was diluted with toluene to prepare a toluene solution having a solid content concentration of 20%.

Comparative Production Examples 1 and 2
Polymerization was carried out in the same manner as in Production Example 1 with the composition shown in Table 1. After polymerization, the solution was diluted with toluene to prepare a toluene solution having a solid content concentration of 20%.

Production Example 8
17 g of tripropylene glycol in a 500 ml poly container, 5 g of C18SHA, 1 g of N-methylol acrylamide, 136 g of pure water, 0.6 g of dimethyldioctadecyl ammonium chloride, 1 g of sorbitan monooleate, 2 g of polyoxyethylene tridecyl ether, polyoxyethylene lauryl ether The mixture was charged with 2.4 g, heated to 80 ° C., stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed for 15 minutes with ultrasonic waves. The emulsified dispersion is transferred to a 500 cc four-necked flask equipped with a nitrogen inlet tube, thermometer, stirrer, and reflux tube, and after substitution with nitrogen, 0.1 g of lauryl mercaptan is added and stirred, and then 2,2-azobis (2- 0.6 g of amidinopropane) dihydrochloride was added, the temperature was raised at 60 ° C., and the reaction was conducted for 4 hours to obtain an aqueous dispersion of a polymer. Thereafter, pure water was added to prepare an aqueous dispersion having a solid content concentration of 20%.

Production Examples 9 to 11
Polymerization was carried out in the same manner as in Production Example 8 with the composition shown in Table 2. After polymerization, the dispersion was further diluted with pure water to prepare a water dispersion having a solid content concentration of 20%.

Production Example 12
In a 500 ml poly container, 30 g of tripropylene glycol, 45 g of C18SHA, 34 g of stearyl acrylate, 1 g of N-methylol acrylamide, 180 g of pure water, 2 g of trimethyloctadecyl ammonium chloride, 2 g of sorbitan monooleate, 2.5 g of polyoxyethylene tridecyl ether, 3.5 g of ethylene lauryl ether was charged, heated to 80 ° C., stirred at 2000 rpm for 1 minute with a homomixer, and then emulsified and dispersed for 15 minutes with ultrasonic waves. The emulsified dispersion was transferred to a 500 ml autoclave and purged with nitrogen, and 0.2 g of lauryl mercaptan and 20 g of vinyl chloride were charged. Further, 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, the temperature was raised at 60 ° C., and reaction was carried out for 4 hours to obtain an aqueous dispersion of a polymer. The dispersion was further diluted with pure water to prepare an aqueous dispersion having a solid concentration of 20%.

Production Examples 13 to 16
The polymerization was carried out in the same manner as in Production Example 12 with the composition shown in Table 2. After polymerization, the dispersion was further diluted with pure water to prepare a water dispersion having a solid content concentration of 20%.

Comparative Production Examples 3 to 4
The polymerization was carried out in the same manner as in Production Example 12 with the composition shown in Table 2. After polymerization, the dispersion was further diluted with pure water to prepare a water dispersion having a solid content concentration of 20%.

Comparative Production Example 5
Polymerization was carried out in the same manner as in Production Example 8 with the composition shown in Table 2. After polymerization, the dispersion was further diluted with pure water to prepare a water dispersion having a solid content concentration of 20%.

The meanings of the abbreviations are as follows.

Test Example 1
The toluene solution 1 having a solid concentration of 20% prepared in Production Example 1 was further diluted with toluene to prepare a treatment liquid having a solid concentration of 1.5%. A polyester cloth (gray) and a nylon cloth (black) were dipped in this treatment liquid, and then lightly centrifuged for about 10 seconds. The wet pick-up was about 65% (polyester cloth) and about 40% (nylon cloth). The treated cloth was passed through a pin tenter at 170 ° C. for 1 minute, dried and cured. The treated cloth was dried overnight at room temperature, and then passed through a pin tenter at 170 ° C. for 1 minute to be heat-treated. The test cloth thus treated was evaluated for water repellency by a water repellency test according to the spray method of JIS L-1092. The water repellency results are shown in Table 3.

Test Examples 2 to 7
The toluene solutions 2 to 7 each having a solid concentration of 20% prepared in Production Examples 2 to 7 are diluted with toluene in the same manner as in Test Example 1 (solid content concentration: 1.5%), and the cloth is treated in the same manner as in Test Example 1 The results of the water repellency test are shown in Table 3.

Comparative test examples 1 and 2
Each toluene solution having a solid concentration of 20% prepared in Comparative Production Examples 1 and 2 was diluted with toluene to a solid concentration of 1.5% in the same manner as in Test Example 1, and a cloth was prepared in the same manner as in Test Example 1. The results of treatment and water repellency test are shown in Table 3.

Test Example 8
The aqueous dispersion 8 having a solid content concentration of 20% prepared in Production Example 8 was further diluted with tap water to prepare a treatment liquid having a solid content concentration of 1.5%. A polyester cloth (gray) and a nylon cloth (black) were dipped in this treatment solution and squeezed with a mangle. The wet pick-up was about 55% (polyester cloth) and about 35% (nylon cloth). The treated cloth was passed through a pin tenter at 170 ° C. for 1 minute, dried and cured.
The test cloth thus treated was evaluated for water repellency by a water repellency test according to the spray method of JIS L-1092. The water repellency results are shown in Table 4.
In addition, the evaluation results of water repellency of the test cloths dried with a tumbler (30 minutes at 60 ° C.) after washing ten times according to JIS L-0217 103 are also shown in Table 4.

Test Examples 9 to 16
The aqueous dispersion having a solid concentration of 20% prepared in Production Examples 9 to 16 was diluted with tap water so that the solid concentration would be 1.5% in the same manner as in Test Example 8, to prepare a treatment liquid. The cloth was treated using this treatment liquid in the same manner as in Test Example 8 and the water repellency test was conducted. The results are shown in Table 4.

Comparative test examples 3 to 5
The aqueous dispersion having a solid content concentration of 20% prepared in Comparative Production Examples 3 to 5 was diluted with tap water to a solid content concentration of 1.5% in the same manner as in Test Example 8 to prepare a treatment liquid. The cloth was treated using this treatment liquid in the same manner as in Test Example 8 and the water repellency test was conducted. The results are shown in Table 4.

Measurement of Gum-Up Rate The results of measuring the gum-up rate for Production Examples 8 to 9 and Comparative Production Examples 3 to 5 are shown in Table 4.

The water repellent composition of the present invention can be used as an external treatment (surface treatment) or an internal treatment. The treatment agent of the present invention can be suitably used for substrates such as textiles and masonry, and imparts excellent water repellency to the substrate.

Claims (12)

1. (1) (a) 2 to 100% by weight of the polymer, the formula:
   

   

   
   [Wherein, R ¹ represents an organic residue having an ethylenically unsaturated polymerizable group,
   R ² is a hydrocarbon group having 7 to 30 carbon atoms,
   R ³ is a hydrocarbon group having 1 to 5 carbon atoms. ]
   The water repellent composition containing the polymer which has a repeating unit derived from the amide group containing monomer shown, and (2) liquid medium.
2. The water repellent composition according to claim 1, wherein in the monomer (a), R ¹ is -C (= O) CR ¹¹ = CH ₂ (R ¹¹ is a hydrogen atom or a methyl group).
3. The polymer (1) further has a repeating unit derived from a polymerizable monomer other than the monomer (a),
   The polymerizable monomer other than the monomer (a) has the formula:
   CH ₂ = CA-T
   [Wherein, A represents a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or an iodine atom,
   T is a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a linear or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a linear or cyclic organic group having 2 to 41 carbon atoms having an ester bond . ]
   The water repellent composition according to claim 1 or 2, which is a compound represented by
4. Polymerizable monomers other than monomer (a) are
   (B) Acrylate ester monomer,
   The water repellent composition according to claim 3, which is at least one selected from the group consisting of (c) a non-fluorine crosslinkable monomer, and (d) a halogenated olefin.
5. Other acrylate ester monomers (b) are
   The repellent agent according to claim 4, which is at least one selected from the group consisting of (b1) an acrylate ester monomer having an aliphatic hydrocarbon group, and (b2) an acrylate ester monomer having a cyclic hydrocarbon group. Liquid medicine composition.
6. The non-fluorine crosslinking monomer (c) is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. The water repellent composition according to item 4.
7. The water repellent composition according to claim 4, wherein the halogenated olefin monomer (d) is at least one selected from the group consisting of vinyl chloride and vinylidene chloride.
8. In the polymer, the amount of the repeating unit (b) is 0 to 200 parts by weight and the amount of the repeating unit (c) is 0 to 50 parts by weight with respect to 100 parts by weight of the monomer (a) The water repellent composition according to any one of claims 4 to 7, wherein the amount of the unit (d) is 0 to 100 parts by weight.
9. The water repellent composition according to any one of claims 1 to 8, wherein the liquid medium (2) is water, an organic solvent or a mixture of water and an organic solvent.
10. The water repellent composition according to any one of claims 1 to 9, which is an external treatment agent or an internal treatment agent.
11. A method of treating a substrate comprising treating the substrate with the water repellent composition according to any one of claims 1 to 10.
12. A method of producing a treated textile product, comprising treating a textile product with the water repellent composition according to any one of claims 1 to 10.